Manufacture and treatment of materials



Patented Dec. 1936 UNITED STATES PATENT OFFlCE MANUFACTURE AND TREATMENT OF MATERIALS Henry Dreyfus, London, England '1 Claims. (01. 18-54 This invention relates to the production of filaments, films, sheets, shaped articles and other products containing organic derivatives of cellulose or other lacquer bases, and also to'the treatment of such products, and it relates particularly to the use in such processes of cyclic ethers obtainable by the condensation of glycerine or other tri-hydric alcohols.

- This application is a division of my application S'. No. 640,529 filed 31st October, 1932.

' The cyclic ether compounds employed according to the present invention may be obtained in any suitable manner, e. g. by treating the tri-hydric alcohol with a dehydrating agent, e. g. sulphuric acid, phosphoric acid, zinc chloride, benzene sulphonic acid, calcium chloride and other agents having a relatively high avidity for water. The above agents may be used to efiect the condensation of the glycerine or other tri-hydric alcohol 0 atrelatively low temperatures, but less powerful dehydrating agents may be used at high temperatures.

I find that it is comparatively easy to ascer-' tain the specific conditions for hehydration in order to produce the cyclic ethers in the case of any particular dehydrating agent, since the cyclic ethers themselves are relatively volatile and may be distilled oil from the reaction mixture in presence or absence of water, while if the 'de-- 0 hydration or condensation is conducted under such conditions as to produce only non-cyclic compounds, for example the diand poly-glycerines, such distillation is not possible, since the compounds formed are practically non-volatile. 35 Further it is possible to conduct the dehydration in stages, and it is noticeable that two distinct types of product may be produced, the one being pletely'condensed product, and therefore if the conditions are adjusted so that the hydroxy body 50 is not removed from the sphere of reaction then the condensationcan be carried further to the completely condensed product. Thus starting with glyce'rine a hydroxy substituted ether may be obtained which may be converted into the com- 56 pletely cyclic diglycerinew-tri-ether. This latter .polymerized vinyl for example polymer-' the substances otthe' present invention is the.

ethers of cellulose. The-substances used accord compound may conveniently be employed for the purpose of the present invention in the form of the fraction boiling at 168-176 C. obtained in manner. A distillation or further distillation is often of advantage. Aldehydic or ketonic byproducts may be suitably removed, as for example by means of, bisulphites, and water may be removed'by means of dehydrating agents and/or with the. aid of substances, such as benzene, toluene and methylene chloride, capable of forming azeotropic mixtures with the water.

Products having similar properties may be produced from mixtures of glycerine or other trihydric alcohol with glycols and/ or aldehydes or ketones, for instance ethylene glycol, propylene glycol, 1.2 or 2.3 butylene glycol, iso-butylene glycol, formaldehyde, acetaldehyde, acrolein, acetone, cyclohexanone and benzaldehyde, and the invention also includes the use of suchproducts;

I find that both types of ether, hydroxy and non-hydroxy, and also the etherified and esterifled hydroxy cyclic ethers, for instance the methylated, ethylated, acetylated, lactylated and formylated derivatives, form a valuable series of solvents and softening or plasticizing agents for a large variety of organic products and notabb' for dyestufls, resins, both natural and artificial, and cellulose esters and ethers, and the present invention includes all such applications. 01' the resins which may be dissolved in or softened or plasticized by the said compounds, I may mention shellac, dammar, the phenol aldehyde fusible soluble synthetic resins, both in the Novolak and Resol stage, and similar resins from other starting materials, for instance from diphenylolpropane and formaldehyde and other aldehydes, from urea or thiourea and formaldehyde, irom glycerine or other polyhydric alcohol and phthalic 45 acid or other poly-carboxylic acid, and also the ized vinyl acetate. However, the most important application or utilization of their solvent properties for cellulose acetate, cellulose nitrate andother esters or' ing to the present invention, and particularly-.

those containing no hydroxy groups or in which .55,

- referred to.

the hydroxy groups have been esterified or etherified, are especially important in dissolving or softening cellulose derivatives of high ester or ether content, particularly those containing more than two substitutent groups per CeHmOs molecule. Thus the above substances have a very good solvent or softening action not only for the commercial acetone-soluble cellulose acetate having an acetyl content of about 52-54%, calculated as acetic acid, but also for the cellulose acetates having a high acetyl content, e. g. 56- 58% or 60%, and even for the tri-acetate having an acetyl content of 62.5%. These discoveries are of particular value since the available solvents for the acetone-soluble cellulose acetates are limited, and those available for the triacetate are very few in number and their use is in general prohibitive since they are toxic chlorine derivatives and are expensive.

The cyclic ethers may be employed in spinning solutions for the manufacture of artificial filaments, ribbons, films, foils, sheets and the like by dry spinning processes. They mayfurther be employed in wet spinning processes, in the actual coagulating baths, as described in U. S. Patent No. 1,467,493,- and British Patents Nos. 340,324 and 340,325, in subsequent treatment baths and/or in the spinning solution as described in British Patent No. 340,324.

In all the above applications the solvents of the present invention may be employed with or without other solvents and/or diluents, for example acetone, methyl acetone, dioxane, dimethylene dioxide, cyclic oxo-ketones, e. g. tetrahydropyrone, methyl acetate, ethyl acetate, butyl acetate, ethers of olefine and polyolefine glycols, methylene chloride, ethylene chloride, dichlorethylene, trichlorethylene, chloroform, alcohols, hydrocarbons and ethers, e. g. isopropyl ether. In the manufacture of spinning solutions and the like it is convenient to employ the new cyclic ethers and their etherified or esterified derivatives with lower boiling solvents, such as those instanced above. Other medium or high boiling solvents or plasticizers may also be incorporated, for example triacetin, diethyl phthalate, dibutyl phthalate, sulphonamides, for example alkylated xylene sulphonamides, sulphonanilides, tartrates, for instance dibutyl tartrate or diphenylol propane or other phenolic plasticizers. Hydroxy compounds, e. g. glycol and glycerine, or other diluents for example toluene, xylene or other relatively cheap hydrocarbons or non-solvents for the cellulose derivatives or other lacquer base may be incorporated m the spinning solutions or the like within the range of tolerance of such solutions. The above compositions may contain any other desired constituents, for instance dyestuffs, pigments or fillers, and cellulose derivative compositions may also contain resins, for example the natural and synthetic resins already The compositions may also, if desired, contain substances adapted to reduce their flammability, as for example halogenated and particularly brominated organic compounds, for

*'-"example tribromacetanilide and other brominated 'acidylated aromatic amines. The substances for reducing flammability may themselves be plasticizers, as in the case of the tribromacetanilide's, in which case they may be used, if desired, none.

The particular .condensation products used according to the present invention may themselves contain halogen atoms, and may thus of themselves exert a fire-retardant action.

As mentioned above, in the case of the production of artificial filaments, ribbons, films and similar materials from solutions containing the condensation products employed according to the present invention, such products will not in general constitute the sole solvent present, since they are mostly compounds of low volatility. Preferably, in the case of dry spinning processes, other volatile liquids are used in conjunction with the condensation products employed according to the present invention, as, for example, acetone or a mixture of acetone and alcohol or mixtures of methylene or ethylene chloride with ethyl or methyl alcohol, and it ispreferable that such more volatile solvents should constitute the major portion of the total solvent. When the materials are produced by wet spinning processes, the low volatility of the condensation products is of less importance, so that they may constitute the sole solvent present in the solution, but it is nevertheless preferable to employ them in conjunction with other more volatile solvents.

In the case of wet spinningprocesses the condensation products may be employed in the spinning solution or in the coagulating or an aftertreatment bath or in any two or more of these media, as described, for example, in U. S. Patent No. 1,467,493 and British Patents Nos. 340,- 324 and 340,325.

In addition to being of value in the working up of cellulose esters and ethers or other lacquer bases into any desired products as described above, the solvents, softening agents and plasticizers of the present invention are also highly valuable for the treatment of already formed articles, particularly those made of or containing cellulose derivatives, for example filaments, yarns, threads, ribbons, films, fabrics and the like. Such treatments may have various objects. For example the tendency of woven fabrics to slip and of warp or circular knitted fabrics to split or ladder may be diminished or eliminated by treatment with the solvents of the present invention in the manner described in U. S. Patent No. 1,935,263. The new agents may be used to improve the pliability of filaments, threads and the like and in particular to improve the knotting properties of comparatively thick filaments or artificial horsehair, and

to improve the extension of filaments, threads, yarns and the like, by effecting treatment with the solvents without stretching and preferably with shrinking. This latter application is particularly important in relation to the treatment of filaments or the like of low extension produced by wet spinning processes, and filaments or the like of low extension produced by the stretching of dry spun products. Such shrinking processes are described broadly in British Patent No. 389,823. The cyclic compounds may also be used in the production of shrinkage effects, as described for example in British Pat-.

applied to the already formed goods. Thus a suitable proportion may be incorporated in the spinning solution and the whole spun by dry spinning processes. The stretching treatment may be applied in one operation and preferably gradually or may be applied in .a number of stages, as described in British Patent No. 370,- 340. Again, as is described in said British patent, the filaments or other products may be stretched while in warp formation by applying a stretching force to the warp as a whole, and this method is particularly advantageous from the point of producing regularity of stretch and also for reasons of economy.

Further, for the treatment of filaments, yarns and the like sizes may be made up containing the new solvents or softening agents so as to eflect a lubrication of the yarns, particularly for facilitating textile operations, such as winding, winding and twisting, beaming and the like. Such sizes may be made' up with or without suitable thickening agents, such as polymerizedvinyl compounds, or oxidized linseed oil or other drying oils. I

i The solvents or softening agents are also of importance in processes involving the absorption of various liquid or solid materials by filaments, yarns, threads, ribbons, films, fabrics and the like containing cellulose esters or ethers or other lacquer bases. For example such products may be treated with the solvents during or before loading processes-or processes designed to modify the appearance of thematerials, e. g. before or during a treatment'adapted to dye, print, mordant, or apply delustering compounds to the materials, the absorbtion of the dyes, loading agents, mordanting agents and delustering compounds being facilitated or rendered. possible by the aid of the solvents. Thus a large number of solid agents have little or no'afiinity for cellulose acetate and by the use of the compounds employed according to the present invention such substances may be incorporated in the materials by dyeing, printing,

stencilling, mechanical impregnation or other methods. Examples of such substances are certain basic dyestuffs having relatively little affinity, particularly in printing processes, acid wool and direct cotton dyestuffs, certain vat dyestuffs, white and coloured pigments, for example titanium dioxide, and certain discharges, for example, formaldehyde sulphoxylate discharges. Again, in printing and similar operations it is usual to fix the dyestufi or other agent in the material by means of a steaming or ageing treatemployed in processes designed to relustre fabrics or other materials, particularly those containing cellulose acetate or other organic esters or ethers, which have been delustered by the action of moist steam or of hot aqueous media, and reference is made in this connection to U. S. Patent No. 1,80 8,098. The relustering may be effected uniformly over the whole of the material or merely locally so as to produce an effect fabric, for exaid of a suitable thickening agent and drying in order to relustre the material in the printed portions. Dyestuffs, pigments, discharges or other efiect materials may be incorporated in the printing paste containing the cyclic ether compound.

In all the above applications of the solvents or orwhere their solvent power is too great they may be mixed with suitable diluents, for example hydrocarbon diluents of the aliphatic, aromatic or ample, by printing on the cyclic ether with the cyclo-aliphatic series, ethers, alcohols, water or the like. Furthermore the solvents may of course be mixed with other solvents. I

The agents of the present invention are particularly important in relation to the manufacture of artificial silk, yarns, ribbons, foils, films and the like, and the treatment of filaments, yarns, fabrics and other formed products of cellulose acetate, but may also be applied to the manufacture and treatment of similar products of cellulose formate, cellulose propionate, cellulose butyrate, nitro acetate (of low nitrogen content) Example 1 The following is an example of the use of a solution containing the cyclic ethers of the present invention in the production of artificial filaments.

A solution containing Parts Cellulose acetate 100 Acetone 800 Methyl-ether of the mono-acetate of diglycerine di-ether 30 to 40 is spun through suitable orifices into an evaporative atmosphere at a temperature of 60 to C.

The filaments produced may be drawn out to fine denier and in order to assist in this they may before complete drying be carried round light rollers, glass rods or the like in order to'provide a resistance beyond which a further stretch maybe applied.

Example 2- A 23 to 25% solution of cellulose acetate in acetone containing 5% of water is-extruded into a coagulating bath consisting of a 25-35% solution ofthe tri-ether of di-glycerine in alcohol,

water or a mixture of alcohol and water and after emerging from the coagulating bath the filaments are taken through a guide to a rotat-' ing roller and drawn out at a speed of from 50 i cording to this example may contain from 2 to' 4% of the cyclic ether body.

The di-glycerine tri-ether employed in the I above example is thefractio'n boiling at 168-176 C.

obtained in the condensation of glycerol in .the presence of acid dehydrating agents.

Example 3 Filaments or yarns of cellulose acetate in hank or other suitable form are soaked for from 2 to 5 minutes in an aqueous, alcoholic or aqueous- Y alcoholic bath containing 30 to 40% of the compound obtained by condensing glycerol with 1:2 propylene glycol. They are then stretched to the desired extent, for example by 100% or more of their original length, the operation being preferably carried out slowly. By providing a bath of suitable length and if desired, slightly increasing the concentration of the cyclic ether, the stretching operation may be applied to travelling filaments, as for example filaments in warp formation.

Example 4 The following is an example of a printing operation in which the cyclic ethers used according to the present invention are employed. A fabric consisting of cellulose acetate yarn, either delustred or of normal lustre, is printed with the following printing paste:

Parts Dyestuif or pigment 2 to? Diethylene glycol; 12 to 15 Water 30 The methyl ether of the condensation product of glycol and glycerine 40 to 100 Gum arabic 1:1 80 to 120 The dyestuff may be atypical cellulose'acetate dyestuff, for example a dyestuif of the aminoanthraquinone series of a nitro-di-arylamine, or it may be an acid wool or direct cotton dyestuff. Alternatively, if desired a pigment, for example titanium dioxide may be used. After printing,

the fabric is dried at a temperature of 85 to 95 C. for sufficient time to cause the glycerine ether to evaporate audit is then washed with warm water at 50 C. in a solution containing 2 /2 grams of soap per litre and finally rinsed. When a delustred fabric is used and the printing paste includes a dyestuff the lustre upon the printed "areas is restored.

What I claim and desire to secure by Letters Patent is:-

involving extruding a solution of said cellulose acetate into a setting medium, the step of effecting the setting of said solution by passing the extruded material into a liquid medium containing a cyclic ether obtainable by condensing a trihydroxy alcohol with an alcohol containing at least two and less than four hydroxy groups.

3. In the manufacture of artificial filaments, threads, yarns, ribbons, foils and like materials having a basis of cellulose acetate of acetyl content at least 56% by a process" involving extruding a solution of said cellulose acetate into a setting medium, the step of effecting the setting of said solution by passing the extruded material into a liquid medium containing diglycerine triether in the form of the fraction boiling at 168-l76 C. obtained by the condensation of glycerol in the presenceofan acid dehydrating agent.

4. In the manufacture of artificial filaments, threads, yarns, ribbons, foils and like materials having a basis of an organic derivative of cellulose by a process involving the operations of softening and stretching said materials, the step of effecting said softening operation by means of a stretch assisting medium containing a cyclic ether obtainable by condensing a trihydroxy alcohol' with an alcohol containing at least two and not more than four hydroxy groups.

5. In the manufacture of artificial filaments, threads, yarns, ribbons foils and like materials having a basis of cellulose acetate by a process involving the operations of softening and stretching said materials, the step of effecting said softening operation by means of a stretch assisting medium containing di-glycerine triether in the form of the fraction boiling at 'l68-176 C. obtained by the condensation of glycerol in the presence of an acid dehydrating agent.

6. In the manufacture of artificial filaments,

. threads, yarns, ribbons, foils and like materials having a basis of an organic derivative of cellulose by a process involving the operation of shrinking said materials, the step of effecting said operation by means of a shrinking medium containing a cyclic ether obtainable by condensing a trihydroxy alcohol with an alcohol containing at least two and not more than four hydroxy groups. 7. In the manufacture of artificial filaments, threads, yarns, ribbons, foils and like materials having a basis of cellulose acetate by a process involving the operation of shrinking said materials, the step' of eifecting said operation by means of a shrinking medium containing diglycerine triether in the form of the fraction boiling at 168-176 C. obtained by the condensation of glycerol in the presence of an acid dehydrating agent.

HENRY DREYFUS. 

